Plasticized vinyl compounds



Patented June 19, 1945 2,378,753 PLASTICIZE D VINYL COMPOUNDS Gaetano F.DAlelio, Northampton, Mass., assignor to General Electric Company, acorporation of New York No Drawing. Application May 2, 1944, Serial No.533,801

11 Claims. (01. 'zso 3s) The present application is acontinuation-inpart of my copending application Serial No.

405,797, filed August '1, 1941, which application is in turn acontinuation-in-part of my copending application Serial No. 367,117,filed November 25, 1940, now Patent 2,299,741, dated October 27, 1942,both assigned to the assignee of the\ present invention.

This invention relates broadly to new and useful compositions of mattercomprising plasticized vinyl compounds. More particularly the inventionis concerned with compositions comprising polymers and copolymers ofvinyl halides, e. g., polyvinyl chloride, copolymers of vinyl chlorideand vinyl acetate, etc., having incorporated therein a plasticizercomprising essentially a monoor poly-carboxylic ester of a nuclearlyhalogenated, hydroxy aryl compound.

It has been known heretofore that artificial masses or syntheticrubber-like compositions may be made from polymers and copolymers ofvinyl halides by plasticizing such polymeric material with compatibleorganic compounds of low volatility at elevated temperatures. Aplasticizer heretofore widely used for softening polymers and copolymersof vinyl halides is tricresyl phosphate. Although such polymers andcopolymers plasticized with tricresyl phosphate yield satisfactoryproducts for most applications, films produced therefrom discolor atelevated temperatures and lose their flexibility. Moreover, at elevatedtemperatures such films show little or no strength.

I have discovered that the carboxylic esters of nuclearly halogenated,hydroxy aryl compounds act as plasticizers for polymers and copolymersof vinyl halides and impart to such compositions a marked stabilizingeffect at elevated temperatures. Films or thin sheets prepared from suchcompositions are clear, almost colorless or of a light yellow color,flexible, tough, have considerable elasticity and excellent tensilestrength. Furthermore, the presence of the halogen atoms in the arylnucleus of the plasticizer markedly increases the compatibility of theplasticizer with the polymeric vinyl compound and causes the plasticizerto approach a true solution of the one body in the other rather than amere dispersion of the two. components. This improved compatibilitymakes it possible to lessen the miling time, or to use lower millingtemperatures, or both, with obvious advantages, in compounding theplasticizer with the vinyl halide polymer or copolymer. This increasedcompatibility of the components also makes possible the introduction ofthe plasticizer into the monomer or mixture of monomers, or into thepartial polymers or copolymers, and initiating or completing thepolymerization of the polymerizable compound in the presence of theplasticizer. In this way the costly and time-consuming step of millingthe plasticizer with the vinyl halide polymer or copolymer may beeliminated entirely.

Another advantage accruing from the use of the plasticizersherein-described results from the presence of the chemically boundhalogen atoms in the plasticizer. The halogen atoms in the aryl nucleusor the ester increase the molecular weight and boiling point of theester as compared with otherwise identical non-halogenated esters,thereby correspondingly decreasing its vapor pressure. This is a matterof great practical significance. It means that a formed plasticizedcomposition (e. g., a molded article or in the form of extrudedinsulation on a wire or cable) will retain its flexibility andplasticity characteristics over a longer time than otherwise ispossible, since the loss of plasticizer during use of the compositionmaterially is reduced. Another advantage, as compared withheat-non-stable haloaliphatic ester plasticizers, is that heat-stablecompounds that do not evolve halogen under heat constitute theplasticizer. This stability of the halogen present in the plasticizer isdue to the fact that the halogen is attached to the aryl nucleus or ringand, therefore, is split off from the ring much less readily than is analiphatic halogen.

Examples of nuclearly halogenated, hydroxy aryl compounds that may beemployed in forming esters thereof with carboxylic acids, and theresulting esters used as modifiers of vinyl halides in the form ofpolymers and copolymers, are:

(Qatari Para-c or nay] alcohol Ortho-c orbeuzyl alcohol Q-cmorr Meta-cflibslillyl alcohol I CI CW 2,4-dic or nzyl alcohol I clQcmoH Cl2,4,6-trlchlorbenzyl alcohol (IJBI IMO-onion 2-methyl-4-brombenzylalcohol aOcrnomon l ara-fiuoro phenyletliyl alcohol 'Plmnyl,z-chlorbenzyl alcohol l Ocnionlon OrthO-chlorpbenylethyl alcohol-0100110111011 Pora-chlorphenylethyl alcohol 01 CHICHIOH4-chlor-l-naphthylethyl alcohol Para-chlor paradipbenyletbyl alcoholCOCILCH OH Ortho, psrndichlor phenylethy! alcohol Ortho, ortho-dlbromphenylethyl alcohol Any suitable carboxylic acid may be used inpreparing the ester plasticizer.

acids are preferred because of their higher boiling points and sincethey yield esters of lower vapor pressure as compared with themonocarboxylic esters of nuclearly halogenated, hydroxy aryl compounds.When monocarboxylic acids Monocarboxylic .acids may be used but, ingeneral, polycanboxylic with a plasticizer comprising essentially anester derived froma carboxylic acid containing at least two carboxylicroups and at, least six carbon atoms and a nuclearly halogenatedaromatic hydroxy compound containing at least six carbon atoms;illustrative examples of such esters are the 'di-(mono-chlorbenzyl)esters, di-(polychlorbenzyl) esters, etc., e. g., di-(para-chlor-Ibenzyl) sebacate, di-(ortho-chlorbenzyl) adipate, di-(dichlorbenzyl)glutarate, di-(trichlorbenzyl) phthalate, di-(pentachlorbenzyl)sebacate, etc.,

or mixtures thereof, the di-(mono-chlor phenylethyl) esters,di-(polychlor phenylethyl) esters. etc., e. g., di-(para-chlorphenylethyl) sebacate, di-(ortho-chlor phenylethyl) adipate, di-(ortho,para-di-chlor phenylethyl) glutarate, di-(ortho, para-di-chlorphenylethyl) phthalate, di-(4 chlor-l-naphthylethyl) sebacate, di-(p-ch1or-p'- diphenyethyl) sebacate, etc., or mixtures thereof.

The polymers and copolymers of vinyl halides may be plasticized with theherein-described esters alone or in conjunction with other plastlcizerswhen particular properties not otherwise obtained are desired. Varyingamounts of plasticizer may be incorporated into the vinyl halide polymeror copolymer depending, for example. upon the particular startingmaterials employed and the particular properties desired in theendproduct. Ordinarily, however, the proportion of plasticizer does notexceed substantially per This example illustrates generally thepreparation of nuclearly halogenated, hydroxyl aryl com-- poundsemployed in forming the esters.

Preparation of para-chlorphenylethyl alcohol Parts Molar ratioParabromochlorobenzene Magnesium turnlngs The magnesium was covered with200 parts by volume of, anhydrous ether in a suitable vessel fitted withcondenser, sealed stirred and dropping tube. Thirty parts of theparabromochlorobenzene were added and a trace of iodine introducedsolution of 50 parts of ethylene oxide in parts by volume of ether wasadded slowly, after which the mixture was heated under reflux for onehour. It was then decomposed in ice water and dilute sulfuric acid addedto dissolve the magnesium hydroxide. The ether-benzene layer wasseparated and washed with sodium bicarbonate solution and dried overanhydrous sodium sulfate.

The ether and benzene were first distilled oil and the residue wasfractionated at 1.25 mm. pressure. The parachlorphenylethyl alcohol wascollected at 110-114" C. at this pressure.

Ortho-chlorphenylethyl alcohol and the parabromphenylethyl alcohol wereprepared in a manner similar to the pr par tion escribed for thepreparation of para-chlorphenylethyl alcohol. In the case of theortho-chlorphenylethyl alcohol the starting material wasortho-bromochlorobenzene and in the case 01' the para-bromphenylethylalcohol the starting material was para-dibromobenzene.

Examples 2 to 6 illustrate the preparation of typical halogenated esterplasticizers.

EXAXPLE 2 Preparation of di- (para-chlorphenylethyl) sebacate PartsMolar ratio Para-chlorphenylethyl alcohol 9. 2 Sebacic acid 5. 8 1Toluene sulionic acid 0. 75

The above components were dissolved in 60 parts by volume of benzene ina suitable flask equipped with a. reflux condenser and Stark and Deantrap arranged for the continuous removal of water. The mixture washeated for 15 hours followed by vigorous refluxing for more hours. Thebenzene was evaporated on a water bath and the remaining oil cooled. Acrystalline mass was obalcohol yielding white crystalline plates.

Analysis of the ester showed a chlorine content of 14.50% compared witha theoretical value for di-(para-chlorphenylethyl) sebacate of 14.80%.

The melting point of the ester was 62 C, and the saponiiicatlonequivalent was found to be 237.8, which compared with the theoretical of239.6.

EXAMPLE 3- Preparation of di-(ortho-chlorphenylethyl) adipate PartsMolar ratio Ortho-chlpgphenylethyl alcohol Adipic ac Toluene sulfonicacid EXAMPLE 4 Di-(para-chlorphenylethyl) adipate was prepared in amanner similar to that outlined in Example 2, and upon analysis showed achlorine content of 15.93%, as compared to the theoretical value forthis compound of 16.76%. The melting point was 63 C. and thesaponification equivalent was 205.3, as compared to the theoretical of211.6.

* tained which was recrystallized 2-3 times fromDi-(para-chlorphenylethyl) phthalni'e wasgmparedinamannersimilartothatoutlinedinExample 2 and analysis of thiscompound showed a chlorine content of as compa e wi the theoreticalvahie of 16.01%. The compound had a melting point at 72 C. and thesaponiflcation equivalent was foimd to be 219.2 as compared to thetheoretical value of 221.5.

EXAIPLI 6 The following esters were also prepared using the procedureoutlined in Example 2, but substituting for the para-chlorphenylethylalcohol,

para-bromophenylethyl alcohol.

Per cent Saponi- The- Equiv. M. P. (BL) or M D i-(para-bromovahenylethyl) phtha- "C to 06 2o. 73 M. 01 267. 2 260. 0Di-(para-bromo-phenlethyl) adipaie 74 31.12 31. 21 255.2 256. 0(para-bromo-pherr yletliyl) aebacatem 72 27. B 28. i3 270. 3 284. 0

Exam '7 This example illustrates the results obtained when unplasticizedpolyvinyl chloride is sheeted and molded.

Sixty-six parts by weight polyvinyl chloride were sheeted on hot rollsat a temperature corresponding approximately to a steam presure of 20pounds per square inch, working on the rolls being continued for fiveminutes after the first formation of a sheet. The sheet material wasvery dark in color. It was used 1) in preparing a molded test disk and2) for testing the flow of plasticity characteristics after reducing thesheet to the necessary size.

The molded test disk was prepared by molding piece of the broken sheetunder a pressure of 2,000 pounds per square inch and at a temperaturecorresponding to a steam pressure of 180 to 190 pounds per square inchuntil the material softened and the excess flowed from the mold. Steamimmediately was turned oil. the mold and the mold cooled by circulatingwater through the jacket. The molded disk was brittle, opaque, verydark-colored, had a Dynstat flexural strength of only 8,370 pounds persquare inch, a Dynstat impact strength of only 0.055 foot pound and aDynstat angle of bend of only 6.7".

when a small pill of the sheeted polyvinyl chloride was tested for flowcharacteristics on a standard Baekeland flow tester, it required morethan seconds for the material to flow 1 inches at a temperaturecorresponding to 190- pounds steam pressure.

The loss in weight on heating a 2 %-inch square of the sheet material,about-35 or 40 mils thick, in an air oven maintained at a constanttemperature of C. for 22 hours was 1.06%.

Example 7 represents the production of a control sample with which theplasticized compositions described in examples that follow were comparedto evaluate the eiiect of the plasticizer.

Exunmn8 Fifty-ilve parts polyvinyl chloride and 11 parts tricresylphosphate were thoroughly mixed to form a homogeneous composition, whichwas Baekeland flow value color, while the molded disk was even darkerand almost opaque. Test data are given below:

Dynstat flexural strength 6,300 pound per sq. in. Dynstat impactstrength 0.03 foot lbs. Dynstat angle of bend 7 loss on heating for 22hours at at same 43 seconds to temperature as in Ex. 7 flow 1% in.

Comparing the'above tests on the plasticized composition of this examplewith the unplasticiaed composition of Example 7, it will be noted thatalthough the plasticity of the composition has been improved, there is adecrease in the flexural and impact strengths. Furthermore, the loss onheating for 22 hours at 125 C. is increased, due to the volatilizationof the plasticizer, from 1.06% IO-2.97%-

Exauru 9 The same precedure was followed as described under Examples 7and 8 with the exception that 55 parts polyvinyl chloride and 11, partsdl- (orthochlorbenzyl) adipate were mixed, sheeted, molded and tested.Both the sheet material and the molded test disk were clear and light incolor. Test data follow:

It will be noted from a comparison of the results of the tests on thiscomposition with the tricresyl phosphate plasticized composition of'Example 8 that the di-(orthochlorbenzyl) adipate causes a markedincrease in the fiexural and impact strengths and also in the angle 01'bend.

Exuutr 11 fiame procedure as under Examples 7 and 8 with the exceptionthat parts polyvinyl chloride and 11 parts bis-(di-chlorbenzyl)sebacate, more particularly di-(ortho-chloro, para-chloro benzyl)sebacate, were .mixed, sheeted, molded and tested. Both the sheetmaterial and the Here again it will be noted that the flexural andimpact strengths and the angle or bend are markedly better than thetricresyl phosphate plasticlzed composition of Example 8. Even moresurprising is the fact that the results of heating the composition evenfor a longer time (24 hours as compared with 22 hours at 125 C. showed aloss on heating less than that of the plasticizer free blank (0.716% ascompared with 1.06% for the blank, that is, the product of Example 7).The test was carefully checked with substantially the same results.Apparently, in some unexplainable manner, the presence of thedi-(orthochloro, para-chloro benzyl) sebacate inhibits the vaporizationof the polyvinyl chloride component when the composition is subjectedtoelevated temperatures.

. ExAuPLr: 12

. mer or vinyl chloride and vinyl acetate (Vinylite Furthermore, theloss on heating at 125 C. is considerably less (2.16% as compared with2.97%).

EXAMPLE 10 Same procedure as under Examples 7 and 8 with the exceptionthat 55 parts polyvinyl chloride and 11 parts di-(para-chlorbenzyl)sebacate were mixed, sheeted, molded and tested. Both the sheet materialand the molded test disk were clear and light-colored. Test data follow:

Dynstat flexural strength 8,817 pounds per sq. in. Dynstat impactstrength 0.167 ioot lbs. Dynstat angle or bend 14.8 Loss on heating for22 hours at 125 C 1.28% Baekeland flow value at same temperature as inEx. 7 43 seconds to flow 1%ins Comparing the test results on this samplewith those of Example 8, wherein tricresyl phosphate was employed asplasticizer, it will be noted not only that the flexural and impactstrengths and angle of bend is unexpectedly higher, but also that theloss on heating the plasticized composition for 22 hours at 125 C. isonly 1.28% as compared with 1.06% for the non-plasticized blank (productof Example 7) and 2.97% for the polyvinyl halide-tricresyl phosphatecomposition.

V'YNK #74212 produced and sold by Carbide and Carbon ChemicalsCorporation), was employed. Molding of the sheet material caused it todarken considerably. The loss on heating a sample for 30 hours at C. was1.05%. The Baekeland flow value at a temperature corresponding to about50 pounds steam pressure was 60 seconds to flow 1% inches. 1

. ExAurLr: 13

A vinyl chloride-vinyl acetate copolymer (60 parts) such as described inExample 12 was worked on hot rolls to form a continuous sheet at atemperature corresponding to a steam pressure 01.20 pounds per squareinch after which 10 per cent by weight thereof (6 parts) ofdi-(orthochlorbenzyl) adipate was dusted on'the sheet. Thereafter thesheet was worked for five minutes on the rolls to insure complete anduniform' distribution of the plasticizer throughout the mass. A moldedtest disk was prepared as described in Example 7. Both the sheetmaterial and the molded disk wereclear' and very light in color. Theimproved plasticity of the composition is shown by the tact that,whereas the flow value of the unplasticized material (Example 12) was 60seconds, the flow value of this plasticized composition was 33 secondsunder the same test conditions.

EXAMPLE 14 Same as in Example 13 with the exception that 6 partsdi-(para-chlorbenzyll sebacate were used EXAMPLE 15 Same procedure wasfollowed as described in Example 13 with the exception that 6 parts di-(ortho,para-di-chlorbenzyl) sebacate were used in place ofdi-(ortho-chlorbenzyl) adipate. Both the sheet material and the moldeddisk were clear and very light in color. As'in the case oi! the productof Example 11 where polyvinylchloride was employed, here again it wasnoted that heating the composition for even as long as 24 hours at 1250. resulted in a loss even less than that or the plasticizer-free blank(0.47% against 1.05% for the blank, that is, the product of Example 12).The test was carefully checked with substantially the same results. TheBaekeland flow value was 20 seconds as compared with 60 seconds for theunplasticized copolymer. The Dynstat flexural and impact strengths andangle of bend of the plasticized copolymer were practically the same asthe values obtained for the non-plasticized copolymer.

The plasticized compositions of this invention also'have exceptionalflexibilityat low temperatures. For example, when equal parts by weightof polyvinyl chloride (or a copolymer of vinyl chloride and, forinstance, vinyl acetate) are homogeneously mixed with di-(ortho-chlorbenzyl) adipate, di-(para-chlorbenzyl) sebacate ordl-(ortho,para-dichlorbenzyl) sebacate and thin sheets of the sheetedproducts placed in the evaporative unit of an electric refrigerator tora period suflicient to attain the units temperature (20 minutes), theflexibility of the sheet is maintained even at such low temperatures to-15 0., for example). Thus, a copolymer of vinyl chloride and vinylacetate plasticized with 50% by weight thereof oi.di-(ortho,para-dichlorbenzyl) sebacate was so flexible even afterminutes in the evaporative unit of a refrigerator .that it could beturned over on itself around a mandrel of very small diameter (about Mrinch ndiameter). I

Instead of the nuclearly halogenated benzyl a1- cohol esters illustratedin the foregoing examples, nuclearly halogenated aryl ethyl alcoholesters may be advantageously substituted using, for example, esters ofsuch alcohols as are illustrated in the table on pages 1 and 2 andillustrated in Examples 1 to 6.

01 course, it will be understood by those skilled in the art that myinvention is not limited to the specific components named in the aboveillustrative examples nor to the specific proportions therein given.Thus, instead of polyvinyl chloride, other polyvinyl halides may beemployed, forv example, polyvinyl bromide or polyvinyl iodide.

Compositions comprising polyvinyl iodide should be avoided whereresistance to discoloration ,at elevated temperatures is important.Also, instead of a copolymer of vinyl chloride and vinyl acetate, I mayuse a copolymer of a vinyl halide and any other organic compoundcopolymerizable therewith, for example, copolymers of vinyl chloride-andvinylidene halides, specifically vinylideiie chloride; copolymers ofvinyl chloride and vinyl hexoate; copolymers oi! vinyl halides and vinylethers; copolymers of vinyl halides and vinyl ketones; copolymers ofvinyl halides and itaconic esters such, for instance, as dipropylitaconate, dibenzyl itaconate, diisoamyl itaconate, etc.; copolymers 0!vinyl halides and acrylic and alkacrylic compounds, for example, methylacrylate, ethyl acrylate, propyl acrylate, phenyl acrylate,benzyl-acrylate, chlorbenzyl acrylates, cyclohexyl acrylate, cresylacrylate, phenethyl acrylate, tetrahydrofurturyl acrylate, ethylmethacrylate, methoxyethyl acrylate, methyl atropate, atropi'c nitrile,etc.; copolymers of a vinyl halide and a diene, e. a copolymer of vinylchloride and2-chlorobutadiene-L3; etc. I prefer to use copolymers suchas described and claimed, for example, in my copending applicationSerial No. 367,116, filed November 25, 1940, now Patent 2,299,740'datedOctober 27, 1942, and assigned to the same assignee as the presentinvention; that is, the copolymerization product of a polymerizablemixture comprising essentially vinyl halide, specifically vinyllchlorideand an arylalkanol ester of acrylic acid, specifically a benzyl (or amonoor poly-chlorbenzyl) acrylate. Such copolymers also may contain,where improved solvent resistance is desired, not over 0.5% by weight ofa polymerizable compound containing a plurality of polymerizablegroupings at least one of which is a on o l I, I h

newcompositions with heat, light and electrical stabilizers as comparedwith the previously known,

plasticized polymers and copolymers of vinyl halides. The most effectiveclass of stabilizers are the leadv derivatives of phenol and substitutedphenols, that is, hydroxy aryl compounds, for example, cresols,xylenols, salicyclic esters, napththols, etc. Lead para-chloro phenate,lead phenyl phenate and lead tertiary amyl phenates are particularlyadapted to the stabilization oi! the plasticized compositions of thisinvention. Cadmium derivatives oi! hydroxy aryl compounds alsomighbehemeriifiiyed.

e er -descr' ed compositions com ris (1? the product of p lymerizationof a 11185500 55 prising essentially a vinyl halide and (2) a carboxylicester of a nuclearly halogenated, hydroxy aryl compound have a widevariety of industrial applications. Thus, with or without fillers, e.g., asbestos, they may be used as insulation material, for instance, asinsulation for electrical conductors. The extrudable compositions may beextruded at temperatures 01' the order of to C. upon a conducting core,e, g., a copper wire, or the soluble compositions may be applied in theform 01 a varnish'and the varnish baked upon the wire. They also may beemployed in the production oi molding compositions and molded articles,as adhesives, coating and impreg ester 01' a nuclear-lyhalogenated arylethyl alcohol. Y 2. 'A composition comprising (1) the product 01'polymerization of a mass comprising essentially a vinvl halide and (2) apolycarboxylic acid polyester of a nuclearly halogenated phenylethylalcohol. t I

3. A composition comprising (1) the product of polymerization oil a masscomprising essentially vinyl chloride and (2) a nuclearly halogenatedphenylethyl alcohol polyester of a polycarboxylic acid. I

4. A composition comprising (1) the product of polymerization of a masscomprising essentially vinyl chloride and (2) a nuclearly ch10- rinatedphenylethyl alcohol diester of a dicarboxylic acid.

5. A composition comprising (1) the product of polymerization of a masscomprising a vinyl halide and an aryl ester of an acrylic acidcontaining a Y grouping and (2) a polycarhoxylic acid polyester oi anuclearly halogenated aryl ethyl alcohol.

Patent No. 2,578,755,".

GAETANO F. DIALELIO.

CERTIFICATE OF CORRECTION.

. boxylic acid.

' chlorphenylethyl) sebacate,

6. A composition comprising (1) the product of polymerization of a masscomprising vinyl chloride and an 'arylalkanol ester of acrylic-acid and(2) a plasticizer for said polymerization product co'mprisingapolycarboxylic acid polyester oi a nuclearly chlorinated phenylethylalcohol.

'1. A compositioncomprising a copolymer of vinyl chloride and anaryialkanol ester of acrylic acid plasticized with a nuclearlychlorinated phenylethyl alcohol diester of a. dicarboxylic acid.

vinyl chloride and an arylalkanol ester. of acrylic acid plasticizedwith a mixture ofnuclearly ch10 rinated phenylethyl alcohol diesters ota dicar- 10. A' composition. comprising (1) the product oipolymerization of a mass comprising vinyl chloride'and benzyl acrylat"and (2) a plasticizer forsaid polymerization product comprising di-(ortho-chlorphenylethyl) adipate.

11. A composition comprising (1) the product of polymerization of a masscomprising vinyl chloride and benzyl acrylate and (2) a plasticizer forsaid polymerization product comprising di-(para- GAE'lANO n'smuo.

June 19, 191

It is hereby certifiedthaterror appears in the printed specificationof'the above mimbered patent requiring correction as follows: Pagel,firstcolumn, line 50, 'for "miling" read- --milling--; page 2, secondcolumn, line 56, for "stirred'. read -stirrer--; page 14., secondcolumn, line 50, for "1%" 1 read ---1---;

and that the. said Letters Patent should be read with this correctiontherein that:- the same may conform to the record of the case in the Patent- Office Signed and sealed this 25th day of September, A. n. 19L 5.

(Seal) Leslie Frazer First Assistant Commissioner of Patents.

molded articles, as adhesives, coating and impreg ester 01' anuclear-lyhalogenated aryl ethyl alcohol. Y 2. 'A composition comprising(1) the product 01' polymerization of a mass comprising essentially avinvl halide and (2) a polycarboxylic acid polyester of a nuclearlyhalogenated phenylethyl alcohol. t I

3. A composition comprising (1) the product of polymerization oil a masscomprising essentially vinyl chloride and (2) a nuclearly halogenatedphenylethyl alcohol polyester of a polycarboxylic acid. I

4. A composition comprising (1) the product of polymerization of a masscomprising essentially vinyl chloride and (2) a nuclearly ch10- rinatedphenylethyl alcohol diester of a dicarboxylic acid.

5. A composition comprising (1) the product of polymerization of a masscomprising a vinyl halide and an aryl ester of an acrylic acidcontaining a Y grouping and (2) a polycarhoxylic acid polyester oi anuclearly halogenated aryl ethyl alcohol.

Patent No. 2,578,755,".

GAETANO F. DIALELIO.

CERTIFICATE OF CORRECTION.

. boxylic acid.

' chlorphenylethyl) sebacate,

6. A composition comprising (1) the product of polymerization of a masscomprising vinyl chloride and an 'arylalkanol ester of acrylic-acid and(2) a plasticizer for said polymerization product co'mprisingapolycarboxylic acid polyester oi a nuclearly chlorinated phenylethylalcohol.

'1. A compositioncomprising a copolymer of vinyl chloride and anaryialkanol ester of acrylic acid plasticized with a nuclearlychlorinated phenylethyl alcohol diester of a. dicarboxylic acid.

vinyl chloride and an arylalkanol ester. of acrylic acid plasticizedwith a mixture ofnuclearly ch10 rinated phenylethyl alcohol diesters ota dicar- 10. A' composition. comprising (1) the product oipolymerization of a mass comprising vinyl chloride'and benzyl acrylat"and (2) a plasticizer forsaid polymerization product comprising di-(ortho-chlorphenylethyl) adipate.

11. A composition comprising (1) the product of polymerization of a masscomprising vinyl chloride and benzyl acrylate and (2) a plasticizer forsaid polymerization product comprising di-(para- GAE'lANO n'smuo.

June 19, 191

It is hereby certifiedthaterror appears in the printed specificationof'the above mimbered patent requiring correction as follows: Pagel,firstcolumn, line 50, 'for "miling" read- --milling--; page 2, secondcolumn, line 56, for "stirred'. read -stirrer--; page 14., secondcolumn, line 50, for "1%" 1 read ---1---;

and that the. said Letters Patent should be read with this correctiontherein that:- the same may conform to the record of the case in the Patent- Office Signed and sealed this 25th day of September, A. n. 19L 5.

(Seal) Leslie Frazer First Assistant Commissioner of Patents.

